08 Chapter1
08 Chapter1
08 Chapter1
1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 1.10 1.11 1.12 1.13
Composites - General Introduction Historical Background Classification of Composites Short fiber- Rubber Composites Constituents of short fiber-rubber composites Reinforcing Mechanism of Short Fibers Factors affecting the properties of Short fiber- Rubber Composites Multicomponent system Nanocomposites Silica Application of Nanosilica / Short fiber / Elastomeric hybrid Composites Scope and objectives of the present work References
1.1
materials known to men. Progresses in the field of materials science and technology have given birth to these fascinating and wonderful materials. Composites are heterogeneous in nature, created by the assembly of two or more components with fillers or reinforcing fibers and a compactable matrix [1]. The matrix may be metallic, ceramic or polymeric in origin. It gives the composites their shape, surface appearance, environmental tolerance and overall durability while the fibrous reinforcement carries most of the structural loads thus giving macroscopic stiffness and strength [2]. A composite material can provide superior and unique mechanical and physical properties because it combines the most desirable properties of its constituents while suppressing their least desirable properties. At present composite materials play a key role in aerospace industry, automobile industry and other engineering applications as they exhibit outstanding
C o n t e n t s
Chapter-1
strength to weight and modulus to weight ratio. High performance rigid composites made from glass, graphite, kevlar, boron or silicon carbide fibers in polymeric matrices have been studied extensively because of their application in aerospace and space vehicle technology [3-8]. Based on the matrix material which forms the continuous phase, the composites are broadly classified into metal matrix (MMC), ceramic matrix (CMC) and polymer matrix (PMC) composites. Of these, polymer matrix composites are much easier to fabricate than MMC and CMC. This is due to the relatively low processing temperature required for fabricating polymer matrix composite. PMCs generally consist of synthetic fibers like carbon, nylon, rayon or glass embedded in a polymer matrix, which surrounds and tightly binds the fibers. Typically, the fibers make up about 60 % of a polymer matrix composite by volume. The structure, properties and applications of various composites are being investigated world wide by several researchers [9 -18]. The fibrous reinforcing constituent of composites may consist of thin continuous fibers or relatively short fiber segments. When using short fiber segments, fibers with high aspect ratio (length to diameter ratio) are used. Continuous fiber reinforced composites are generally required for high performance structural applications. The specific strength (strength to density ratio) and specific stiffness (modulus to density ratio) of continuous carbon fiber reinforced composites can be superior to conventional metal alloys. Also depending upon how fibers are oriented within the matrix, composites can be fabricated into products that have structural properties specifically tailored for a particular use. Polymer concretes are increasingly being used in buildings and other structures. They represent a new type of structural material capable of withstanding highly corrosive environments. The high strength to weight ratio and non-corrosive characteristics of these materials like fiber-reinforced plastics can be utilised to build innovative structures, which are, desirable and economical [19].
Introduction
Although composite materials have certain advantages over conventional materials, they have some disadvantages also. PMCs and other composite materials tend to be anisotropic; that is, properties like strength, stiffness etc. are different in different directions depending on the orientation of composite constituent materials. These anisotropic properties pose a significant challenge for the designer who uses composite materials in structures that place multi-directional forces on structural members. Also formation of a strong connection between the components of the composite material is difficult. The broader use of advanced composites is inhibited by high manufacturing costs. Development of advanced composite materials having superior mechanical properties opened up new horizons in the engineering field. The advantages such as corrosion resistance, electrical insulation, low thermal expansion, higher stiffness, strength and fatigue resistance make them preferred candidates for many applications [20-25].
1.2
Historical Background
Nature has provided composite materials in living things such as seaweeds,
bamboo, wood and human bone. The first reinforced polymeric based materials appear to have been used by the people of Babylonia around 4000-2000 B.C. The materials consisted of reinforced bitumen or pitch. Around 3000 B.C. evidences from various sources indicate that in Egypt and Mesopotamia, types of river-boat were constructed from bundles of papyrus reed embedded in a matrix of bitumen. The art of mummification that flourished in Egypt during 2500 B.C.exemplifies one of the first filament winding process. Suitably treated dead bodies were wrapped in tapes of linen and then impregnated with a natural resin to produce, ultimately a rigid cocoon. The use of lac has been known to India and China for several thousands of years. It is recorded in the Vedas written about 1000 B.C. In India the resin was used as filling for swords hafts and in the manufacture of whetstones by mixing shellac with fine sand. The latter example may be considered as the forerunner of the modern composite
Chapter-1
grinding wheel. By 500 B.C., the Greeks were building ships with three banks of oars called triremes. They possessed keels that were much longer than could have been accomplished by using a single length of timber. Thus, it can be seen that the origin of composite technology goes back into antiquity. The relative importance of the structural materials most commonly used, i.e. metals, polymers, composites, and ceramics, to various societies throughout history has fluctuated. Ashby [26] presents a chronological variation of the relative importance of each group from 10,000 B.C. and extrapolates their importance through the year 2020. The information contained in Ashbys article has been partially reproduced in Figure 1.1. The importance of composites has experienced a steady growth since about 1960 and is projected to continue to increase through the next several decades. The fiber-reinforced polymer market is estimated at almost 1.04 million metric tons (2.3 billion lbs) in 2002, and is expected to increase by 15 % in volume [27]. According to the above report, the market for fiber-reinforced polymers will grow at an average annual growth rate (AAGR) of 3.0 % through the next five years, increasing to 1.2 million tons per year by 2010.
Introduction
1.3
Classification of Composites
Based on the types of reinforcement used, the composites are classified as
1.3.1 Particulate reinforced composites A composite whose reinforcement is a particle with all the dimensions roughly equal are called particulate reinforced composites. Particulate fillers are employed to improve high temperature performance, reduce friction, increase wear resistance and to reduce shrinkage [28]. The particles will also share the load with the matrix, but to a lesser extent than a fiber. A particulate reinforcement will therefore improve stiffness but will not generally strengthen. 1.3.2 Fiber reinforced composites Fiber reinforced composites contain reinforcements having lengths higher than cross sectional dimension. Fibrous reinforcement represents physical rather than a chemical means of changing a material to suit various engineering applications [29]. These can be broadly classified as
Chapter-1
Reinforcing fiber in a single layer composite may be short or long based on its overall dimensions. Composites with long fibers are called continuous fiber reinforcement and composite in which short or staple fibers are embedded in the matrix are termed as discontinuous fiber reinforcement (short fiber composites). In continuous fiber composites fibers are oriented in one direction to produce enhanced strength properties. In short fiber composites, the length of short fiber is neither too high to allow individual fibers to entangle with each other nor too small for the fibers to loss their fibrous nature. The reinforcement is uniform in the case of composites containing well dispersed short fibers. There is a clear distinction between the behavior of short and long fiber composites. 1.3.3 Hybrid composites Composite materials incorporated with two or more different types of fillers especially fibers in a single matrix are commonly known as hybrid composites. Hybridisation is commonly used for improving the properties and for lowering the cost of conventional composites. There are different types of hybrid composites classified according to the way in which the component materials are incorporated. Hybrids are designated as i) sandwich type ii) interply iii) intraply and iv) intimately mixed [30]. In sandwich hybrids, one material is sandwiched between layers of another, whereas in interply, alternate layers of two or more materials are stacked in regular manner. Rows of two or more constituents are arranged in a regular or random manner in intraply hybrids while in intimately mixed type, these constituents are mixed as much as possible so that no concentration of either type is present in the composite material. 1.3.4 Laminates A laminate is fabricated by stacking a number of laminae in the thickness direction. Generally three layers are arranged alternatively for better bonding between reinforcement and the polymer matrix, for example plywood and paper.
6
Introduction
These laminates can have unidirectional or bi-directional orientation of the fiber reinforcement according to the end use of the composite. A hybrid laminate can also be fabricated by the use of different constituent materials or of the same material with different reinforcing pattern. In most of the applications of laminated composite, man made fibers are used due to their good combination of physical, mechanical and thermal behavior.
1.4
length which is neither too high to allow individual fibers to entangle with each other, nor too low for the fibers to lose their fibrous characteristics. A short fiber composite signifies that the two main constituents, i.e., the short fibers and the rubber matrix remain recognizable in the designed material. When used properly, a degree of reinforcement can be generated from short fibers, which is sufficient for many applications.
Interface Fiber
Matrix
Short fiber reinforced rubber composites were developed to fill the gap between the long fiber reinforced and particulate filled rubber composites. That is mainly to achieve the high performance of the fiber coupled with easy processability and
Chapter-1
elasticity of the rubber. Composites in which the short fibers are oriented uniaxially in an elastomer have a good combination of good strength and stiffness from the fibers and elasticity from the rubber. These composites are being used for the fabrication of a wide variety of products such as V-belts, hoses and articles with complex shapes [3132]. Short fiber reinforced rubber composites possess several advantages over continuous fiber composites [33-36]. Short fibers can be easily incorporated into the rubber compound along with other ingredients. They are amenable to standard rubber processing operations such as extrusion, calendaring, compression molding, injection molding etc. These composites provide high green strength and high dimensional stability during fabrication. Design flexibility is another advantage of these composites. Complex shaped articles which is quite difficult to accomplish with long fiber composites can be fabricated using short fiber composites. Mechanical properties like specific strength and stiffness, reduced shrinkage in molded products, resistance to solvent swelling, abrasion, tear and creep resistance are greatly improved in the case of short fiber composites. Moreover short fibers are cheaper than long fibers. But there are some disadvantages also. Difficulty in achieving uniform dispersion, fiber breakage during processing, difficulties in handling and bonding etc. are some among them. One of the first reports on short fiber reinforcement of rubber, natural rubber was used by Collier [37] as the rubber matrix, which was reinforced using short cotton fibers. Though NR, the most commonly used elastomeric matrix for short fiber reinforcement, styrene butadiene rubber (SBR), chloroprene rubber (CR), nitrile rubber (NBR) and ethylene propylene rubber (EPDM) also received attention [38- 44].These rubbers were reinforced using short fibers such as cotton, silk, rayon,jute and Nylon [45- 50]. Mingtao Run et al. [51] studied crystal morphology and nonisothermal crystallization kinetics of short carbon fiber/ poly(trimethylene terephthalate) composites. Relationship between processing method and microstructural and
Introduction
mechanical properties of poly(ethylene terephthalate) / short glass fiber composites were studied by Mondadori et.al. [52]. Das et al. [53] reinforced bromobutyl rubber using short Kevlar fiber. Zuev [54] studied the mechanical properties of fiber-filled rubber composites and ways of effective utilization of mechanical properties of fibers in fiber filled rubber composites and compared with those of rubber compound in the absences of fibers. Maya et al. [55] presented a review on cellulosic fiber-reinforced green composites. Short Nylon fiber reinforced polypropylene was studied by Thomas et al.[56]. Anuar and co workers [57] studied the tensile and impact properties of thermoplastic natural rubber reinforced short glass fiber and empty fruit bunch hybrid composites. In a review, Kun [58] presented the effect of type of fiber, fiber pretreatment, compounding and processing on the product performance properties. Advances in short fiber pretreatment, interfacial adhesion and development of short fiber- rubber composite products were reviewed by Zhou et al. [59]. Fiber reinforced plastic and rubber composites for electrical insulators have been manufactured by Kadowaki [60]. Wazzan [61] studied the physico-mechanical properties of EPDM/ Nylon-6 short fiber composites. Dynamic mechanical behavior of short coir fiber reinforced natural rubber composites was studied by Geethamma et al. [62]. In the case of soft rubbery composites cellulose fiber has been found to give better reinforcement than glass or carbon fibers [63]. Atomic force microscopy (AFM) studies of short melamine fiber reinforced EPDM rubber was done by Rajeev et al.[64]. Short jute fiber reinforced NR composites have been studied by Murty et al. [65].Investigations have also been made on short jute fiber reinforced carboxylated nitrile rubber [66]. Cure characteristics and mechanical properties of short Nylon 6 fiber nitrile rubber composites were studied by Rajesh et al. [67]. Natural rubbercoir fiber composite was studied by Geethamma et al [68-69]. A novel method for the preparation of short Nylon fiber-natural rubber composites was developed by Bipinbal et al. [13], in which short fibers chopped to approximately 6 mm were
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Chapter-1
incorporated in the latex stage and processed into sheet form. By this method, mixing cycle time was reduced without compromising the fiber dispersion. Fiber breakage during mixing was also reduced. Effect of processing parameters on the mechanical properties of short Kevlar aramid fiber- thermoplastic PU composite were reported by Kutty et al. [70]. Kutty et al. [71] also studied the reinforcement of millable PU with short Kevlar fiber. The mechanical properties of short fiber polymer composites and the influence of surface treatment of short fiber have also been investigated [72-75].The possibility of using natural fibers as reinforcement in polymer based composites has been examined [76-80]. Studies on composites containing short banana fibers and polyester resin have been conducted [81-83]. Effect of short fiber diameter on mechanics of rubber composites was studied by Zhang et al. [84]. Rheological properties of short polyester fiber polyurethane elastomer composites with and without bonding agent was reported by Suhara et al. [85 - 86]. Suhara et al. [87] also studied the thermal degradation of short polyester fiber- polyurethane elastomer composite and found that incorporation of short fiber enhanced the thermal stability of the elastomer.
1.5
Typically, the matrix has considerably lower density, stiffness and strength than those of the reinforcing fiber material, but the combination of matrix and fiber produces high strength and stiffness, while still possessing a relatively low density. In a composite the matrix is required to fulfill the following functions: To bind together the fibers by virtue of its cohesive and adhesive characteristics To protect them from environments and handling.
10
Introduction